Catalyst

ABSTRACT

A catalyst in solid particulate form free from an external carrier material comprising
         (I) a complex of formula (I)       

     
       
         
         
             
             
         
       
         
         
           
             wherein 
             M is zirconium or hafnium; 
             each X is a sigma ligand; 
             L is a divalent bridge selected from —R′ 2 C—, —R′ 2 C—CR′ 2 —, —R′ 2 Si—, —R′ 2 Si—SiR′ 2 —, —R′ 2 Ge—, wherein each R′ is independently a hydrogen atom, C1-C20-alkyl, tri(C1-C20-alkyl)silyl, C6-C20-aryl, C7-C20-arylalkyl or C7-C20-alkylaryl; 
             each R 2  is independently hydrogen or a C1-C20 hydrocarbyl radical provided that at least one R 2  is not hydrogen; 
             each R 5  is independently hydrogen or a C1-20 hydrocarbyl group optionally containing one or more heteroatoms from groups 14-16; 
             each R 6  is independently hydrogen or a C1-20 hydrocarbyl group optionally containing one or more heteroatoms from groups 14-16; 
             each n is independently 1, 2 or 3; and 
             each R 8  is a C1-20 hydrocarbyl group; 
             and (ii) a cocatalyst comprising a compound of a group 13 metal, e.g. Al or boron.

FIELD OF INVENTION

This invention relates to new bisindenyl catalysts, in particular, solidparticulate racemic symmetrical metallocene catalysts containing suchbisindenyl ligands. The invention also relates to the use of such newbisindenyl metallocene catalysts for the production of polypropylene atexcellent catalyst activities to give polypropylene with high molecularweight, and very high melting point even at industrially relevantpolymerization temperatures.

BACKGROUND OF INVENTION

Metallocene catalysts have been used to manufacture polyolefins for manyyears. Countless academic and patent publications describe the use ofthese catalysts in olefin polymerisation. Metallocenes are now usedindustrially and polyethylenes and polypropylenes in particular areoften produced using cyclopentadienyl based catalyst systems withdifferent substitution patterns. The two most important physicalproperties of isotactic polypropylene (iPP) are its average molecularweight and its melting point (Tm), the latter being mostly determined bythe degree of stereoregularity (isotacticity) of the polypropylenechains.

The Ziegler-Natta catalyst systems known in the literature can produceiPP with high molecular weights together with moderate to highisotacticities and melting temperatures (Tm). The Tm (measured bystandard DSC methods) of non-nucleated iPPs are in the range of 160 to165° C.

In the case of metallocenes, there are very few examples which canproduce iPP having both very high molecular weights and high meltingpoints. For example rac-Et(2,4,7-Me₃Ind)₂ZrCl₂ can produce isotacticpolypropylene with a molecular weight of 1,900,000 g/mol and a meltingpoint of 168° C.

In order to achieve such high values, a polymerization temperature of−30° C. is necessary. When the polymerization temperature is increasedto 30° C., the melting point of the resulting polypropylene decreases to158° C. A polymerization temperature of −30° C. is however, far too lowfor polypropylene manufacturing in commercial plants, which need to beoperated above 60° C. When used at industrially useful polymerizationtemperatures, this same metallocene yields low molecular weightpolypropylenes with relatively low melting point. For example at 70° C.,rac-Et(2,4,7-Me₃Ind)₂ZrCl₂/MAO yields a polypropylene of molecularweight of only 30,600 with a melting point of only 145° C.

In U.S. Pat. No. 7,405,261, rac-Et[2,7-Me₂-4-(4-tBuPh)Ind]₂ZrCl₂ isreported to produce iPP with a melting point of 156° C., by polymerizingliquid propylene at 65° C.

WO2009/054831 describes zirconocenes with a 2-methyl-4,7-arylsubstitution pattern, such as rac-Me₂Si[2-Me-4,7-(4-tBuPh)₂Ind]₂ZrCl₂.The melting points of the homopolymers are still quite low, being in allcases below 150° C. despite the relatively low polymerizationtemperature of 65° C.

WO02/02576 describes conventionally supported metallocenes such asrac-Me₂Si[2-Me-4-(3,5-tBu₂Ph)Ind]₂ZrCl₂. These metallocene catalysts,activated with MAO or a borate, on a silica support, at a polymerisationtemperature of 60 or 70° C., give iPP with Tm between 156 and 159° C.

The metallocene rac-9-silafluorenyl-9,9-[2-Me-4-(3,5-tBu₂Ph)Ind]₂ZrCl₂also gives high melting point iPP and are described in WO02/02575.

In general however, metallocene catalysts, when used under industriallyrelevant polymerization conditions, produce iPP having melting pointswhich are lower than the melting points of Ziegler Natta iPP, and eventhe best metallocene catalysts produce iPP with melting points of lessthan 160° C. In addition, few metallocene catalysts can produce iPPhaving both high melting point and high molecular weight atpolymerisation temperatures above 60° C.

In order to overcome this inherent limitation of metallocene catalysts,and in order to produce polypropylenes having both high melting pointsand high molecular weights, we have developed a new family of catalystscomprising substituted bis-indenyl complexes.

Whilst the bisindenyl complexes of this invention are known, we employthese complexes in solid particulate yet unsupported form to make a newfamily of catalysts with interesting properties. These metallocenes havebeen found to produce isotactic polypropylenes with surprisingly highmelting points and very high molecular weights.

The catalysts of the invention comprise a bridged bisindenyl metallocenecomplex with a substituted aryl group at the 4-position of an indenylligand and at least one non hydrogen substituent at the 2-position ofthe ring. The seven position is unsubstituted. Such complexes are knownin the art in WO02/02576. However, the metallocene catalysts ofWO02/025676, activated with MAO or a borate, are carried on a silicasupport. At polymerisation temperatures of 60 or 70° C. they give iPPwith Tm between 156 and 159° C. but at very poor catalyst activity.

The present inventors sought a new catalyst system capable of producing,inter alia, isotactic polypropylene with high melting points, highisotacticity and high molecular weights without compromising catalystactivity at commercially relevant temperatures.

SUMMARY OF INVENTION

Thus, viewed from one aspect the invention provides a catalyst in solidparticulate form free from an external carrier material comprising

(i) a complex of formula (I)

wherein

M is zirconium or hafnium;

-   -   each X is a sigma ligand;

L is a divalent bridge selected from —R′₂C—, —R′₂C—CR′₂—, —R′₂Si—,—R′₂Si—SiR′₂—, —R′₂Ge—, wherein each R′ is independently a hydrogenatom, C1-C20-alkyl, tri(C1-C20-alkyl)silyl, C6-C20-aryl,C7-C20-arylalkyl or C7-C20-alkylaryl;

each R₂ is independently hydrogen or a C1-C20 hydrocarbyl radicalprovided that at least one R₂ is not hydrogen;

each R₅ is independently hydrogen or a C1-20 hydrocarbyl groupoptionally containing one or more heteroatoms from groups 14-16;

each R₆ is independently hydrogen or a C1-20 hydrocarbyl groupoptionally containing one or more heteroatoms from groups 14-16;

each n is independently 1, 2 or 3;

each R₈ is a C1-20 hydrocarbyl group.

and (ii) a cocatalyst comprising a compound of a group 13 metal, e.g. Alor boron.

Ideally, the catalyst is obtainable by a process in which

(a) a liquid/liquid emulsion system is formed, said liquid/liquidemulsion system comprising a solution of the catalyst components (i) and(ii) dispersed in a solvent so as to form dispersed droplets; and

(b) solid particles are formed by solidifying said dispersed droplets.

Viewed from another aspect the invention provides a process for themanufacture of a catalyst as hereinbefore defined comprising obtaining acomplex of formula (I) and a cocatalyst as hereinbefore described;

forming a liquid/liquid emulsion system, which comprises a solution ofcatalyst components (i) and (ii) dispersed in a solvent, and solidifyingsaid dispersed droplets to form solid particles.

Viewed from another aspect the invention provides the use in olefinpolymerisation of a catalyst as hereinbefore defined.

Viewed from another aspect the invention provides a process for thepolymerisation of at least one olefin, in particular propylene,comprising polymerising said at least one olefin with a catalyst ashereinbefore described.

Viewed from another aspect the invention provides a process forproducing an isotactic polypropylene with a melting point of at least155° C. and at a catalyst activity of at least 10.0 kg/g(cat)/hcomprising polymerising propylene in the presence of the catalyst ashereinbefore defined.

DEFINITIONS

Throughout the description the following definitions are employed.

By free from an external carrier is meant that the catalyst does notcontain an external support, such as an inorganic support, for example,silica or alumina, or an organic polymeric support material, onto whichcatalyst components are loaded.

The term C₁₋₂₀ hydrocarbyl group includes C₁₋₂₀ alkyl, C₂₋₂₀ alkenyl,C₂₋₂₀ alkynyl, C₃₋₂₀ cycloalkyl, C₃₋₂₀ cycloalkenyl, C₆₋₂₀ aryl groups,C₇₋₂₀ alkylaryl groups or C₇₋₂₀ arylalkyl groups or of course mixturesof these groups such as cycloalkyl substituted by alkyl.

Unless otherwise stated, preferred C₁₋₂₀ hydrocarbyl groups are C₁₋₂₀alkyl, C₄₋₂₀ cycloalkyl, C₅₋₂₀ cycloalkyl-alkyl groups, C₇₋₂₀ alkylarylgroups, C₇₋₂₀ arylalkyl groups or C₆₋₂₀ aryl groups, especially C₁₋₁₀alkyl groups, C₆₋₁₀ aryl groups, or C₇₋₁₂ arylalkyl groups, e.g. C₁₋₈alkyl groups. Most especially preferred hydrocarbyl groups are methyl,ethyl, propyl, isopropyl, tertbutyl, isobutyl, C₅₋₆-cycloalkyl,cyclohexylmethyl, phenyl or benzyl.

The term halo includes fluoro, chloro, bromo and iodo groups, especiallychloro groups, when relating to the complex definition.

The term heterocyclic group means a preferably monocyclic non aromaticring structure comprising at least one heteroatom, e.g. piperidinyl orpiperazinyl.

The term heteroaryl means a preferably monocyclic aromatic ringstructure comprising at least one heteroatom. Preferred heteroarylgroups have 1 to 4 heteroatoms selected from O, S and N. Preferredheteroaryl groups include furanyl, thiophenyl, oxazole, thiazole,isothiazole, isooxazole, triazole and pyridyl.

Any group including “one or more heteroatoms belonging to groups 14-16”preferably means O, S or N. N groups may present as —NH— or —NW— whereR″ is C1-10 alkyl. There may, for example, be 1 to 4 heteroatoms. Thatheteroatom might be at the end or in the middle of the group inquestion, e.g. forming O—Me.

The oxidation state of the metal ion is governed primarily by the natureof the metal ion in question and the stability of the individualoxidation states of each metal ion.

It will be appreciated that in the complexes of the invention, the metalion M is coordinated by ligands X so as to satisfy the valency of themetal ion and to fill its available coordination sites. The nature ofthese 6-ligands can vary greatly.

Catalyst activity is defined in this application to be the amount ofpolymer produced (kg)/g catalyst/h. Catalyst metal activity is definedhere to be the amount of polymer produced (kg)/g Metal/h. The termproductivity is also sometimes used to indicate the catalyst activityalthough herein it designates the amount of polymer produced per unitweight of catalyst.

DETAILED DESCRIPTION OF INVENTION

The catalysts of the invention comprise a complex of formula (I)

wherein

M is zirconium or hafnium;

each X is a sigma ligand;

L is a divalent bridge selected from —R′₂C—, —R′₂C—CR′₂—, —R′₂Si—,—R′₂Si—SiR′₂— and —R′₂Ge—, wherein each R′ is independently a hydrogenatom, C1-C20-alkyl, tri(C1-C20-alkyl)silyl, C6-C20-aryl,C7-C20-arylalkyl or C7-C20-alkylaryl;

each R₂ is independently hydrogen or a C1-C20 hydrocarbyl radicalprovided that at least one R₂ is not hydrogen;

each R₅ is independently hydrogen or a C1-20 hydrocarbyl groupoptionally containing one or more heteroatoms from groups 14-16;

each R₆ is independently hydrogen or a C1-20 hydrocarbyl groupoptionally containing one or more heteroatoms from groups 14-16;

each n is independently 1, 2 or 3;

each R₈ is a C1-20 hydrocarbyl group.

The catalyst of the invention is not in supported form but is in solidparticulate form. The term solid implies that the catalyst is solid atroom temperature. The term particulate implies that the catalyst is afree flowing powder like material.

The two multicyclic ligands making up the complexes of the invention arepreferably identical and hence the complexes of the invention may besymmetrical. The complexes of the invention are preferably in theirracemic form. It is a feature of the invention, that the processdescribed in detail below for the formation of the complexes of theinvention gives rise to complexes predominantly in their rac form.

There is low or very low meso form of the complexes formed, e.g. lessthan 20 wt % thereof.

M is preferably Zr.

Each X, which may be the same or different, is preferably a hydrogenatom, a halogen atom, a R, OR, OSO₂CF₃, OCOR, SR, NR₂ or PR₂ groupwherein R is a linear or branched, cyclic or acyclic, C1-C20-alkyl,C2-C20 alkenyl, C2-C20 alkynyl, C6-C20-aryl, C7-C20-alkylaryl orC7-C20-arylalkyl radical; optionally containing heteroatoms belonging togroups 14-16. R is preferably a C₁₋₆ alkyl, phenyl or benzyl group.

Most preferably each X is independently a hydrogen atom, a halogen atom,C₁₋₆-alkoxy group or an R group, e.g. preferably a C₁₋₆-alkyl, phenyl orbenzyl group. Most preferably X is chlorine or a methyl radical.Preferably both X groups are the same.

In any L group, it is preferred if all R′ groups are the same. L ispreferably a bridge comprising a heteroatom, such as silicon or,germanium, e.g. —SiR⁹ ₂—, wherein each R⁹ is independently C1-C20-alkyl,C5-10 cycloalkyl, C6-C20-aryl or tri(C1-C20-alkyl)silyl-residue, such astrimethylsilyl. More preferably R⁹ is C₁₋₆-alkyl, especially methyl. Itis preferred if all R⁹ groups are the same. Most preferably, L is adimethylsilyl or diethylsilyl bridge. It may also be an ethylene ormethylene bridge.

R₂ is preferably a C1-10 hydrocarbyl group such as C1-6-hydrocarbylgroup. More preferably it is a linear or branched C1-20 alkyl group.More preferably it is a linear or branched C1-6 alkyl group, especiallylinear C1-6 alkyl group such as methyl or ethyl. Ideally R₂ is methyl.

At least one R₈ group is present on the Ph rings. It is preferred if allR₈ groups are the same. It is preferred however, if 2 such groups arepresent, i.e. n is 2. In particular, those groups should be positionedat the 3 and 5 positions of the Ph ring bound to the indenyl ligand.

R₈ is preferably a C1-20 hydrocarbyl group, such as a C1-20 alkyl groupor C6-10 aryl group. R₈ groups can be the same or different, preferablythe same. More preferably, R₈ is a C2-10 alkyl group such as C3-8 alkylgroup. Highly preferred groups are tert butyl groups. It is preferred ifthe group R₈ is bulky, i.e. is branched. Branching might be alpha orbeta to the Ph ring. Branched C3-8 alkyl groups are also favouredtherefore.

Each R₅ is preferably hydrogen or a C1-10 alkyl group, such as methyl.Ideally R₅ is hydrogen.

Each R₆ is preferably hydrogen or a C1-10 alkyl group, such as methyl.Ideally R₆ is hydrogen.

Preferred complexes of the invention are therefore of formula (II)

wherein

M is zirconium or hafnium;

each X is a sigma ligand, preferably each X is independently a hydrogenatom, a halogen atom, C₁₋₆-alkoxy group, C₁₋₆-alkyl, phenyl or benzylgroup;

L is a divalent bridge selected from —R′₂C—, —R′₂C—CR′₂—, —R′₂Si—,—R′₂Si—SiR′₂—, —R′₂Ge—, wherein each R′ is independently a hydrogenatom, C1-C20-alkyl, tri(C1-C20-alkyl)silyl, C6-C20-aryl,C7-C20-arylalkyl or C7-C20-alkylaryl; preferably dimethylsilyl,methylene or ethylene;

each R₂ is a C1-10 alkyl group;

each R₅ is hydrogen or a C1-10 alkyl group;

each R₆ is hydrogen or a C1-10 alkyl group;

n is 1 to 3, e.g. 2;

and each R⁸ is a C1-20 hydrocarbyl group.

Still more preferred complexes of the invention are of formula (III):

wherein

M is zirconium or hafnium;

each X is a sigma ligand, preferably each X is independently a hydrogenatom, a halogen atom, C₁₋₆-alkoxy group, C₁₋₆-alkyl, phenyl or benzylgroup;

L is a divalent bridge selected from —R′₂C—, —R′₂C—CR′₂—, —R′₂Si—,—R′₂Si—SiR′₂—, —R′₂Ge—, wherein each R′ is independently a hydrogenatom, C1-C20-hydrocarbyl, tri(C1-C20-alkyl)silyl, C6-C20-aryl,C7-C20-arylalkyl or C7-C20-alkylaryl; preferably dimethylsilyl;

R₂ is preferably a C1-10 alkyl group;

n is 1 to 3, e.g. 2;

and each R⁸ is a C1-10 alkyl group or C6-10 aryl group.

Still more preferred complexes of the invention are of formula (IV)

wherein L, M and X are as hereinbefore defined (e.g. in formula (III));

R₂ is methyl; and

R₈ is C3-8 alkyl.

Highly preferred complexes of the invention are

rac-Me₂Si[2-Me-4(3,5-^(t)Bu₂Ph)-Ind]₂ZrCl₂.

rac-Me₂Si[2-Me-4(3,5-^(t)Bu₂Ph)-Ind]₂HfCl₂.

For the avoidance of doubt, any narrower definition of a substituentoffered above can be combined with any other broad or narroweddefinition of any other substituent.

Throughout the disclosure above, where a narrower definition of asubstituent is presented, that narrower definition is deemed disclosedin conjunction with all broader and narrower definitions of othersubstituents in the application.

Synthesis

The ligands required to form the complexes and hence catalysts of theinvention can be synthesised by any process and the skilled organicchemist would be able to devise various synthetic protocols for themanufacture of the necessary ligand materials. In particular WO02/02576describes suitable synthetic protocols.

Ideally, the Ph group at the 4-position should carry at least twosubstituents, in particular substituents such as methyl, iso-propyl,neopentyl, tert-butyl or phenyl. Ideally, such bulky substituents are inthe 3,5-positions of the 4-substituent. Ideally they are tert-butylgroups.

A conventional synthesis for ligands of formula (I) is given inWO02/02576. The key indene ligand precursor is shown in Scheme 1 belowfor the most preferred ligand uses herein:

The present inventors have devised a new procedure for the formation ofthis key intermediate which forms a further aspect of the invention.

The new procedure is shown in Scheme 2:

The first step of this “one-pot” sequence is a Ni-catalyzed Kumadacoupling, where the bromine atom in the indene 6-membered ring getssubstituted with a di(tert-butyl)phenyl moiety). In order to obtain anindene i.e. formally eliminate MeOH and form a carbon-carbon doublebond, an acid-catalyzed elimination using a dean-stark apparatus isused. TsOH can be used as an acid catalyst and toluene can be employedto remove water/methanol azeotropically

This process seems to lead to a much higher yield of key intermediate.

Thus, viewed from another aspect the invention provides a process forthe preparation of a compound of formula (V):

comprising at least the step of reacting a compound of formula (VI)

with a compound (VII)

wherein R₂, R₅, R₆, R₈ and n are as herein before defined, e.g. as informulae (I) to (IV); and

Hal is a halide, preferably Br;

in the presence of PPh₃IPrNiCl₂

In this reagent, IPr represents1,3-bis(2,6-diisopropylphenyl)imidazolidin-2-ylidene. It is believedthat other related imidazolidin-2-ylidene carbenes could also be usedinstead, e.g. those with groups other than1,3-bis(2,6-diisopropylphenyl) such as 1,3-bis(2,4,6-trimethylphenyl).It will be appreciated that the reaction can take place in a solventsuch as THF.

Preferably, this process further comprises a step of contacting thereaction product of compounds (VI) and (VII) with an acid catalyst suchas tosyl alcohol. Again, that reaction can take place in a solvent suchas toluene.

The alkoxy group in formula (VI) is preferably MeO—. The halide ispreferably Br.

It will be appreciated that the ligand formed in this process ispreferably that required to form the catalysts of formula (II), (III) or(IV). In a most preferred embodiment the ligand is

Cocatalyst

To form an active catalytic species it is normally necessary to employ acocatalyst as is well known in the art. Cocatalysts comprising anorganometallic compound of Group 13 metal, like organoaluminiumcompounds used to activate metallocene catalysts are suitable for use inthis invention.

The olefin polymerisation catalyst system of the invention thereforecomprises (i) a complex of the invention; and normally (ii) an aluminiumalkyl compound (or other appropriate cocatalyst), or the reactionproduct thereof. Thus the cocatalyst is preferably an alumoxane, likeMAO or an alumoxane other than MAO.

Alternatively, however, the catalysts of the invention may be used withother cocatalysts, e.g. boron compounds. It will be appreciated by theskilled man that where boron based cocatalysts are employed, it isnormal to preactivate the complex by reaction thereof with an aluminiumalkyl compound, such as TIBA. This procedure is well known and anysuitable aluminium alkyl, e.g. Al(C₁₋₆-alkyl)₃. can be used.

Boron based cocatalysts of interest include those of formula

BY₃

wherein Y is the same or different and is a hydrogen atom, an alkylgroup of from 1 to about 20 carbon atoms, an aryl group of from 6 toabout 15 carbon atoms, alkylaryl, arylalkyl, haloalkyl or haloaryl eachhaving from 1 to 10 carbon atoms in the alkyl radical and from 6-20carbon atoms in the aryl radical or fluorine, chlorine, bromine oriodine. Preferred examples for Y are methyl, propyl, isopropyl, isobutylor trifluoromethyl, unsaturated groups such as aryl or haloaryl likephenyl, tolyl, benzyl groups, p-fluorophenyl, 3,5-difluorophenyl,pentachlorophenyl, pentafluorophenyl, 3,4,5-trifluorophenyl and3,5-di(trifluoromethyl)phenyl. Preferred options are trifluoroborane,triphenylborane, tris(4-fluorophenyl)borane,tris(3,5-difluorophenyl)borane, tris(4-fluoromethylphenyl)borane,tris(2,4,6-trifluorophenyl)borane, tris(penta-fluorophenyl)borane,tris(tolyl)borane, tris(3,5-dimethyl-phenyl)borane,tris(3,5-difluorophenyl)borane and/or tris(3,4,5-trifluorophenyl)borane.

Particular preference is given to tris(pentafluorophenyl)borane.

It is preferred however if borates are used, i.e. compounds containing aborate 3+ ion. Such ionic cocatalysts preferably contain anon-coordinating anion such as tetrakis(pentafluorophenyl)borate andtetraphenylborate. Suitable counterions are protonated amine or anilinederivatives such as methylammonium, anilinium, dimethylammonium,diethylammonium, N-methylanilinium, diphenylammonium,N,N-dimethylanilinium, trimethylammonium, triethylammonium,tri-n-butylammonium, methyldiphenylammonium, pyridinium,p-bromo-N,N-dimethylanilinium or p-nitro-N,N-dimethylanilinium.

Preferred ionic compounds which can be used according to the presentinvention include: triethylammoniumtetra(phenyl)borate,tributylammoniumtetra(phenyl)borate,trimethylammoniumtetra(tolyl)borate, tributylammoniumtetra(tolyl)borate,tributylammoniumtetra(pentafluorophenyeborate,tripropylammoniumtetra(dimethylphenyl)borate,tributylammoniumtetra(trifluoromethylphenyl)borate,tributylammoniumtetra(4-fluorophenyl)borate,N,N-dimethylcyclohexylammoniumtetrakis(pentafluorophenyl)borate,N,N-dimethylbenzylammoniumtetrakis(pentafluorophenyl)borate,N,N-dimethylaniliniumtetra(phenyl)borate,N,N-diethylaniliniumtetra(phenyl)borate,N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate,N,N-di(propyl)ammoniumtetrakis(pentafluorophenyl)borate,di(cyclohexyl)ammoniumtetrakist(pentafluorophenyl)borate,triphenylphosphoniumtetrakis(phenyl)borate,triethylphosphoniumtetrakis(phenyl)borate,diphenylphosphoniumtetrakis(phenyl)borate,tri(methylphenyl)phosphoniumtetrakis(phenyl)borate,tri(dimethylphenyl)phosphoniumtetrakis(phenyl)borate,triphenylcarbeniumtetrakis(pentafluorophenyl)borate, orferroceniumtetrakis(pentafluorophenyl)borate. Preference is given totriphenylcarbeniumtetrakis(pentafluorophenyl)borate,N,N-dimethylcyclohexylammoniumtetrakis(pentafluorophenyl)borate orN5N-dimethylbenzylammoniumtetrakis(pentafluorophenyl)borate.

The use of B(C₆F₅)₃, C₆H₅N(CH₃)₂H:B(C₆F₅)₄, (C₆H₅)₃C:B(C₆F₅)₄ orNi(CN)₄[B(C₆F₅)₃]₄ ² is especially preferred.

Suitable amounts of borate cocatalyst will be well known to the skilledman.

The use of aluminoxanes, especially MAO, is highly preferred.

Suitable amounts of aluminoxane cocatalyst will be well known to theskilled man. Typically Al to M molar ratios are from 1:1 to 1000:1mol/mol. Preferably when an aluminium alkyl is used as a coctalyst, themolar ratio of the aluminium in the activator to the transition metal inthe complex is from 1 to 500 mol/mol, preferably from 10 to 400 mol/moland in particular from 50 to 400 mol/mol.

Manufacture

The metallocene complex of the present invention can be used incombination with a suitable cocatalyst as a catalyst for thepolymerization of olefins, e.g. in a solvent such as toluene or analiphatic hydrocarbon, (i.e. for polymerization in solution), as it iswell known in the art. Preferably, polymerization of olefins, especiallypropylene, takes place in the condensed phase or in gas phase.

The catalyst of the invention is in solid particulate form butunsupported, i.e. no external carrier is used. In order to provide thecatalyst of the invention in solid form but without using an externalcarrier, it is preferred if a liquid liquid emulsion system is used. Theprocess involves forming dispersing catalyst components (i) and (ii) ina solvent, and solidifying said dispersed droplets to form solidparticles.

In particular, the method involves preparing a solution of one or morecatalyst components; dispersing said solution in an solvent to form anemulsion in which said one or more catalyst components are present inthe droplets of the dispersed phase; immobilising the catalystcomponents in the dispersed droplets, in the absence of an externalparticulate porous support, to form solid particles comprising the saidcatalyst, and optionally recovering said particles.

This process enables the manufacture of active catalyst particles withimproved morphology, e.g. with a predetermined spherical shape andparticle size and without using any added external porous supportmaterial, such as an inorganic oxide, e.g. silica. Also desirablesurface properties can be obtained.

By the term “preparing a solution of one or more catalyst components” ismeant that the catalyst forming compounds may be combined in onesolution which is dispersed to the immiscible solvent, or,alternatively, at least two separate catalyst solutions for each part ofthe catalyst forming compounds may be prepared, which are then dispersedsuccessively to the solvent.

In a preferred method for forming the catalyst at least two separatesolutions for each or part of said catalyst may be prepared, which arethen dispersed successively to the immiscible solvent.

More preferably, a solution of the complex comprising the transitionmetal compound and the cocatalyst is combined with the solvent to forman emulsion wherein that inert solvent forms the continuous liquid phaseand the solution comprising the catalyst components forms the dispersedphase (discontinuous phase) in the form of dispersed droplets. Thedroplets are then solidified to form solid catalyst particles, and thesolid particles are separated from the liquid and optionally washedand/or dried. The solvent forming the continuous phase may be immiscibleto the catalyst solution at least at the conditions (e.g. temperatures)used during the dispersing step.

The term “immiscible with the catalyst solution” means that the solvent(continuous phase) is fully immiscible or partly immiscible i.e. notfully miscible with the dispersed phase solution.

Preferably said solvent is inert in relation to the compounds of thecatalyst system to be produced. Full disclosure of the necessary processcan be found in WO03/051934 which is herein incorporated by reference.

The inert solvent must be chemically inert at least at the conditions(e.g. temperature) used during the dispersing step. Preferably, thesolvent of said continuous phase does not contain dissolved therein anysignificant amounts of catalyst forming compounds. Thus, the solidparticles of the catalyst are formed in the droplets from the compoundswhich originate from the dispersed phase (i.e. are provided to theemulsion in a solution dispersed into the continuous phase).

The terms “immobilisation” and “solidification” are used hereininterchangeably for the same purpose, i.e. for forming free flowingsolid catalyst particles in the absence of an external porousparticulate carrier, such as silica. The solidification happens thuswithin the droplets. Said step can be effected in various ways asdisclosed in said WO03/051934 Preferably solidification is caused by anexternal stimulus to the emulsion system such as a temperature change tocause the solidification. Thus in said step the catalyst component (s)remain “fixed” within the formed solid particles. It is also possiblethat one or more of the catalyst components may take part in thesolidification/immobilisation reaction.

Accordingly, solid, compositionally uniform particles having apredetermined particle size range can be obtained.

Furthermore, the particle size of the catalyst particles of theinvention can be controlled by the size of the droplets in the solution,and spherical particles with a uniform particle size distribution can beobtained.

The invention is also industrially advantageous, since it enables thepreparation of the solid particles to be carried out as a one-potprocedure. Continuous or semicontinuous processes are also possible forproducing the catalyst.

Dispersed Phase

The principles for preparing two phase emulsion systems are known in thechemical field. Thus, in order to form the two phase liquid system, thesolution of the catalyst component (s) and the solvent used as thecontinuous liquid phase have to be essentially immiscible at leastduring the dispersing step. This can be achieved in a known manner e.g.by choosing said two liquids and/or the temperature of the dispersingstep/solidifying step accordingly.

A solvent may be employed to form the solution of the catalyst component(s). Said solvent is chosen so that it dissolves said catalyst component(s). The solvent can be preferably an organic solvent such as used inthe field, comprising an optionally substituted hydrocarbon such aslinear or branched aliphatic, alicyclic or aromatic hydrocarbon, such asa linear or cyclic alkane, an aromatic hydrocarbon and/or a halogencontaining hydrocarbon.

Examples of aromatic hydrocarbons are toluene, benzene, ethylbenzene,propylbenzene, butylbenzene and xylene. Toluene is a preferred solvent.The solution may comprise one or more solvents. Such a solvent can thusbe used to facilitate the emulsion formation, and usually does not formpart of the solidified particles, but e.g. is removed after thesolidification step together with the continuous phase.

Alternatively, a solvent may take part in the solidification, e.g. aninert hydrocarbon having a high melting point (waxes), such as above 40°C., suitably above 70° C., e.g. above 80° C. or 90° C., may be used assolvents of the dispersed phase to immobilise the catalyst compoundswithin the formed droplets.

In another embodiment, the solvent consists partly or completely of aliquid monomer, e.g. liquid olefin monomer designed to be polymerised ina “prepolymerisation” immobilisation step.

Continuous Phase

The solvent used to form the continuous liquid phase is a single solventor a mixture of different solvents and may be immiscible with thesolution of the catalyst components at least at the conditions (e.g.temperatures) used during the dispersing step. Preferably said solventis inert in relation to said compounds.

The term “inert in relation to said compounds” means herein that thesolvent of the continuous phase is chemically inert, i.e. undergoes nochemical reaction with any catalyst forming component. Thus, the solidparticles of the catalyst are formed in the droplets from the compoundswhich originate from the dispersed phase, i.e. are provided to theemulsion in a solution dispersed into the continuous phase.

It is preferred that the catalyst components used for forming the solidcatalyst will not be soluble in the solvent of the continuous liquidphase. Preferably, said catalyst components are essentially insoluble insaid continuous phase forming solvent.

Solidification takes place essentially after the droplets are formed,i.e. the solidification is effected within the droplets e.g. by causinga solidifying reaction among the compounds present in the droplets.Furthermore, even if some solidifying agent is added to the systemseparately, it reacts within the droplet phase and no catalyst formingcomponents go into the continuous phase.

The term “emulsion” used herein covers both bi- and multiphasic systems.

In a preferred embodiment said solvent forming the continuous phase isan inert solvent including a halogenated organic solvent or mixturesthereof, preferably fluorinated organic solvents and particularly semi,highly or perfluorinated organic solvents and functionalised derivativesthereof. Examples of the above-mentioned solvents are semi, highly orperfluorinated hydrocarbons, such as alkanes, alkenes and cycloalkanes,ethers, e.g. perfluorinated ethers and amines, particularly tertiaryamines, and functionalised derivatives thereof. Preferred are semi,highly or perfluorinated, particularly perfluorinated hydrocarbons, e.g.perfluorohydrocarbons of e.g. C3-C30, such as C4-C10. Specific examplesof suitable perfluoroalkanes and perfluorocycloalkanes includeperfluoro-hexane, -heptane, -octane and -(methylcyclohexane). Semifluorinated hydrocarbons relates particularly to semifluorinatedn-alkanes, such as perfluoroalkyl-alkane.

“Semi fluorinated” hydrocarbons also include such hydrocarbons whereinblocks of —C—F and —C—H alternate. “Highly fluorinated” means that themajority of the —C—H units are replaced with —C—F units.“Perfluorinated” means that all —C—H units are replaced with —C—F units.See the articles of A. Enders and G. Maas in “Chemie in unserer Zeit”,34. Jahrg. 2000, Nr. 6, and of Pierandrea Lo Nostro in “Advances inColloid and Interface Science”, 56 (1995) 245-287, Elsevier Science.

Dispersing Step

The emulsion can be formed by any means known in the art: by mixing,such as by stirring said solution vigorously to said solvent forming thecontinuous phase or by means of mixing mills, or by means of ultra sonicwave, or by using a so called phase change method for preparing theemulsion by first forming a homogeneous system which is then transferredby changing the temperature of the system to a biphasic system so thatdroplets will be formed.

The two phase state is maintained during the emulsion formation step andthe solidification step, as, for example, by appropriate stirring.

Additionally, emulsifying agents/emulsion stabilisers can be used,preferably in a manner known in the art, for facilitating the formationand/or stability of the emulsion. For the said purposes e.g.surfactants, e.g. a class based on hydrocarbons (including polymerichydrocarbons with a molecular weight e.g. up to 10 000 and optionallyinterrupted with a heteroatom(s)), preferably halogenated hydrocarbons,such as semi- or highly fluorinated hydrocarbons optionally having afunctional group selected e.g. from —OH, —SH, NH₂, NR″₂. —COOH, —COONH₂,oxides of alkenes, —CR″═CH₂, where R″ is hydrogen, or C1-C20 alkyl,C2-20-alkenyl or C2-20-alkynyl group, oxo-groups, cyclic ethers and/orany reactive derivative of these groups, like alkoxy, or carboxylic acidalkyl ester groups, or, preferably semi-, highly- or perfluorinatedhydrocarbons having a functionalised terminal, can be used. Thesurfactants can be added to the catalyst solution, which forms thedispersed phase of the emulsion, to facilitate the forming of theemulsion and to stabilize the emulsion.

Alternatively, an emulsifying and/or emulsion stabilising aid can alsobe formed by reacting a surfactant precursor bearing at least onefunctional group with a compound reactive with said functional group andpresent in the catalyst solution or in the solvent forming thecontinuous phase. The obtained reaction product acts as the actualemulsifying aid and or stabiliser in the formed emulsion system.

Examples of the surfactant precursors usable for forming said reactionproduct include e.g. known surfactants which bear at least onefunctional group selected e.g. from —OH, —SH, NH₂, NR″₂. —COOH, —COONH₂,oxides of alkenes, —CR″═CH₂, where R″ is hydrogen, or C1-C20 alkyl,C2-20-alkenyl or C2-20-alkynyl group, oxo-groups, cyclic ethers with 3to 5 ring atoms, and/or any reactive derivative of these groups, likealkoxy or carboxylic acid alkyl ester groups; e.g. semi-, highly orperfluorinated hydrocarbons bearing one or more of said functionalgroups. Preferably, the surfactant precursor has a terminalfunctionality as defined above.

The compound reacting with such surfactant precursor is preferablycontained in the catalyst solution and may be a further additive or oneor more of the catalyst forming compounds. Such compound is e.g. acompound of group 13 (e.g. MAO and/or an aluminium alkyl compound and/ora transition metal compound).

If a surfactant precursor is used, it is preferably first reacted with acompound of the catalyst solution before the addition of the transitionmetal compound. In one embodiment e.g. a highly fluorinated C1-n(suitably C4-30- or C5-15) alcohol (e.g. highly fluorinated heptanol,octanol or nonanol), oxide (e.g. propenoxide) or acrylate ester isreacted with a cocatalyst to form the “actual” surfactant. Then, anadditional amount of cocatalyst and the transition metal compound isadded to said solution and the obtained solution is dispersed to thesolvent forming the continuous phase. The “actual” surfactant solutionmay be prepared before the dispersing step or in the dispersed system.If said solution is made before the dispersing step, then the prepared“actual” surfactant solution and the transition metal solution may bedispersed successively (e.g. the surfactant solution first) to theimmiscible solvent, or be combined together before the dispersing step.

Solidification

The solidification of the catalyst component(s) in the disperseddroplets can be effected in various ways, e.g. by causing oraccelerating the formation of said solid catalyst forming reactionproducts of the compounds present in the droplets. This can be effected,depending on the used compounds and/or the desired solidification rate,with or without an external stimulus, such as a temperature change ofthe system.

In a particularly preferred embodiment, the solidification is effectedafter the emulsion system is formed by subjecting the system to anexternal stimulus, such as a temperature change. Temperature differencesare of e.g. 5 to 100° C., such as 10 to 100° C., or 20 to 90° C., suchas 50 to 90° C.

The emulsion system may be subjected to a rapid temperature change tocause a fast solidification in the dispersed system. The dispersed phasemay e.g. be subjected to an immediate (within milliseconds to fewseconds) temperature change in order to achieve an instantsolidification of the component (s) within the droplets. The appropriatetemperature change, i.e. an increase or a decrease in the temperature ofan emulsion system, required for the desired solidification rate of thecomponents cannot be limited to any specific range, but naturallydepends on the emulsion system, i.a. on the used compounds and theconcentrations/ratios thereof, as well as on the used solvents, and ischosen accordingly. It is also evident that any techniques may be usedto provide sufficient heating or cooling effect to the dispersed systemto cause the desired solidification.

In one embodiment the heating or cooling effect is obtained by bringingthe emulsion system with a certain temperature to an inert receivingmedium with significantly different temperature, e.g. as stated above,whereby said temperature change of the emulsion system is sufficient tocause the rapid solidification of the droplets. The receiving medium canbe gaseous, e.g. air, or a liquid, preferably a solvent, or a mixture oftwo or more solvents, wherein the catalyst component (s) is (are)immiscible and which is inert in relation to the catalyst component (s).For instance, the receiving medium comprises the same immiscible solventused as the continuous phase in the first emulsion formation step.

Said solvents can be used alone or as a mixture with other solvents,such as aliphatic or aromatic hydrocarbons, such as alkanes. Preferablya fluorinated solvent as the receiving medium is used, which may be thesame as the continuous phase in the emulsion formation, e.g.perfluorinated hydrocarbon.

Alternatively, the temperature difference may be effected by gradualheating of the emulsion system, e.g. up to 10° C. per minute, preferably0.5 to 6° C. per minute and more preferably in 1 to 5° C. per minute.

In case a melt of e.g. a hydrocarbon solvent is used for forming thedispersed phase, the solidification of the droplets may be effected bycooling the system using the temperature difference stated above.

Preferably, the “one phase” change as usable for forming an emulsion canalso be utilised for solidifying the catalytically active contentswithin the droplets of an emulsion system by, again, effecting atemperature change in the dispersed system, whereby the solvent used inthe droplets becomes miscible with the continuous phase, preferably afluorous continuous phase as defined above, so that the droplets becomeimpoverished of the solvent and the solidifying components remaining inthe “droplets” start to solidify. Thus the immiscibility can be adjustedwith respect to the solvents and conditions (temperature) to control thesolidification step.

The miscibility of e.g. organic solvents with fluorous solvents can befound from the literature and be chosen accordingly by a skilled person.Also the critical temperatures needed for the phase change are availablefrom the literature or can be determined using methods known in the art,e.g. the Hildebrand-Scatchard-Theorie. Reference is also made to thearticles of A. Enders and G. and of Pierandrea Lo Nostro cited above.

Thus according to the invention, the entire or only part of the dropletmay be converted to a solid form. The size of the “solidified” dropletmay be smaller or greater than that of the original droplet, e.g. if theamount of the monomer used for the prepolymerisation is relativelylarge.

The solid catalyst particles recovered can be used, after an optionalwashing step, in a polymerisation process of an olefin. Alternatively,the separated and optionally washed solid particles can be dried toremove any solvent present in the particles before use in thepolymerisation step. The separation and optional washing steps can beeffected in a known manner, e.g. by filtration and subsequent washing ofthe solids with a suitable solvent.

The droplet shape of the particles may be substantially maintained. Theformed particles may have a mean size range of 1 to 500 μm, e.g. 5 to500 μm, advantageously 5 to 200 μm or 10 to 150 μm. Even a mean sizerange of 5 to 60 μm is possible. The size may be chosen depending on thepolymerisation the catalyst is used for. Advantageously, the meanparticle size of the ready particulate catalysts of the invention are inthe range of 2 to 150 μm, preferably 5 to 120 μm, more preferably 5 to90 μm and especially in the range 10 to 70 μm. The particles areessentially spherical in shape, they have a low porosity and a lowsurface area.

The formation of solution can be effected at a temperature of 0-100° C.,e.g. at 20-80° C. The dispersion step may be effected at −20° C.−100°C., e.g. at about −10-70° C., such as at −5 to 30° C., e.g. around 0° C.

To the obtained dispersion an emulsifying agent as defined above, may beadded to improve/stabilise the droplet formation. The solidification ofthe catalyst component in the droplets is preferably effected by raisingthe temperature of the mixture, e.g. from 0° C. temperature up to 100°C., e.g. up to 60-90° C., gradually. E.g. in 1 to 180 minutes, e.g. 1-90or 5-30 minutes, or as a rapid heat change. Heating time is dependent onthe size of the reactor.

During the solidification step, which is preferably carried out at about60 to 100° C., preferably at about 75 to 95° C., (below the boilingpoint of the solvents) the solvents may preferably be removed andoptionally the solids are washed with a wash solution, which can be anysolvent or mixture of solvents such as those defined above and/or usedin the art, preferably a hydrocarbon, such as pentane, hexane orheptane, suitably heptane. The washed catalyst can be dried or it can beslurried into an oil and used as a catalyst-oil slurry in polymerisationprocess.

All or part of the preparation steps can be done in a continuous manner.Reference is made to WO2006/069733 describing principles of such acontinuous or semicontinuous preparation methods of the solid catalysttypes, prepared via emulsion/solidification method.

Polymerisation

The olefin polymerized using the catalyst of the invention is preferablypropylene or a higher alpha-olefin or a mixture of ethylene and anα-olefin or a mixture of alpha olefins, for example C₂₋₂₀ olefins, e.g.ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octeneetc. The olefins polymerized in the method of the invention may includeany compound which includes unsaturated polymerizable groups. Thus, forexample unsaturated compounds, such as C₆₋₂₀ olefins (including cyclicand polycyclic olefins (e.g. norbornene)), and polyenes, especiallyC₄₋₂₀ dienes, may be included in a comonomer mixture with lower olefins,e.g. C₂₋₅ α-olefins. Diolefins (i.e. dienes) are suitably used forintroducing long chain branching into the resultant polymer. Examples ofsuch dienes include am linear dienes such as 1,5-hexadiene,1,6-heptadiene, 1,8-nonadiene, 1,9-decadiene, etc.

The catalysts of the present invention are particularly suited for usein the manufacture of polypropylene polymers, especially isotacticpolypropylene.

Polymerization in the method of the invention may be effected in one ormore, e.g. 1, 2 or 3, polymerization reactors, using conventionalpolymerization techniques, e.g. gas phase, solution phase, slurry orbulk polymerization.

In general, a combination of slurry (or bulk) and at least one gas phasereactor is often preferred, particularly with the reactor order beingslurry (or bulk) then one or more gas phase reactors.

In case of propylene polymerisation for slurry reactors, the reactiontemperature will generally be in the range 60 to 110° C. (e.g. 60-90°C.), the reactor pressure will generally be in the range 5 to 80 bar(e.g. 20-60 bar), and the residence time will generally be in the range0.1 to 5 hours (e.g. 0.3 to 2 hours). The monomer is usually used asreaction medium.

For gas phase reactors, the reaction temperature used will generally bein the range 60 to 115° C. (e.g. 70 to 110° C.), the reactor pressurewill generally be in the range 10 to 25 bar, and the residence time willgenerally be 0.5 to 8 hours (e.g. 0.5 to 4 hours) The gas used will bethe monomer optionally as mixture with a non-reactive gas such asnitrogen or propane. In addition to actual polymerisation steps andreactors, the process can contain any additional polymerisation steps,like prepolymerisation step, and any further after reactor handlingsteps as known in the art.

Generally the quantity of catalyst used will depend upon the nature ofthe catalyst, the reactor types and conditions and the propertiesdesired for the polymer product. As is well known in the art hydrogencan be used for controlling the molecular weight of the polymer. It isparticularly notable that the catalyst of the present invention performsexceptionally well over a wide range of hydrogen concentration usedduring the polymerisation process, which makes the catalyst beneficialto be used for productions of a wide range of polymers The catalysts areuseful at higher hydrogen concentrations as well with lower hydrogenconcentrations to get polymer with higher molecular weight. The activityof the catalysts of the invention is also very high and the polymerproductivity levels are excellent.

It is a feature of the invention that the claimed catalysts enable theformation of polymers with remarkably high melting temperatures, Tm andwith remarkably high molecular weight. These features can be achieved atcommercially interesting polymerisation temperatures, e.g. 60° C. ormore. It is a preferred feature of the invention that the catalysts ofthe invention are used to polymerise propylene at a temperature of atleast 60° C., preferably at least 65° C., such as at least 70° C. It isalso notable that catalysts of the present invention produce polymerswith high melting temperatures, such as above 156° C. with clearlyhigher activity of the catalyst compared to catalysts of the prior art.

Catalyst activities may be of the order of 10.0 kg/g(cat)/h or more,such as 12 kg/g(cat)/h or more.

The catalysts of the invention enable the formation of high molecularweight polypropylene which also possess high isotacticity. Isotacticityis measured by 13C NMR or also by DSC. Thus, in the case ofpolypropylene homopolymers, isotacticity can be higher than 99.2% mmwhen measured by 13C NMR. When measured by standard DSC, the highisotacticity of the polypropylene homopolymers means a melting point(Tm) higher than 150° C., preferably higher than 152° C., even morepreferably higher than 155° C.

The molecular weight of the polypropylene can be at least 300,000,preferably at least 400,000, especially at least 500,000. However, themolecular weight of the formed polymer is dependent on the amount ofhydrogen employed, as is well known in the art.

Polypropylenes made by the metallocene catalysts of the invention can bemade with MFR₂ values in the whole range of interest, that is from veryhigh (as high as 2000, for example 1000 or 500) to very low, that isfractional values (<1). Hydrogen can be used to manipulate MFR as iswell known.

The polymers made by the catalysts of the invention are useful in allkinds of end articles such as pipes, films (cast, blown and BOPP films),fibers, moulded articles (e.g. injection moulded, blow moulded,rotomoulded articles), extrusion coatings and so on. Film applications,such as those requiring BOPP (bi-oriented polypropylene) film,especially for capacitors are favoured.

The invention will now be illustrated by reference to the followingnon-limiting Examples.

Measurement Methods: ICP Analysis

The elemental analysis of a catalyst was performed by taking a solidsample of mass, M, cooling over dry ice. Samples were diluted up to aknown volume, V, by dissolving in nitric acid (HNO3, 65%, 5% of V) andfreshly deionised (DI) water (5% of V). The solution was then added tohydrofluoric acid (HF, 40%, 3% of V), diluted with DI water up to thefinal volume, V, and left to stabilise for two hours.

The analysis was run at room temperature using a Thermo Elemental iCAP6300 Inductively Coupled Plasma—Optical Emmision Spectrometer (ICP-OES)which was calibrated using a blank (a solution of 5% HNO3, 3% HF in DIwater), and 6 standards of 0.5 ppm, 1 ppm, 10 ppm, 50 ppm, 100 ppm and300 ppm of Al, with 0.5 ppm, 1 ppm, 5 ppm, 20 ppm, 50 ppm and 100 ppm ofHf and Zr in solutions of 5% HNO3, 3% HF in DI water.

Immediately before analysis the calibration is ‘resloped’ using theblank and 100 ppm Al, 50 ppm Hf, Zr standard, a quality control sample(20 ppm Al, 5 ppm Hf, Zr in a solution of 5% HNO3, 3% HF in DI water) isrun to confirm the reslope. The QC sample is also run after every 5thsample and at the end of a scheduled analysis set.

The content of hafnium was monitored using the 282.022 nm and 339.980 nmlines and the content for zirconium using 339.198 nm line. The contentof aluminium was monitored via the 167.079 nm line, when Alconcentration in ICP sample was between 0-10 ppm (calibrated only to 100ppm) and via the 396.152 nm line for Al concentrations above 10 ppm.

The reported values are an average of three successive aliquots takenfrom the same sample and are related back to the original catalyst byinputting the original mass of sample and the dilution volume into thesoftware.

DSC Analysis

Melting temperature T_(m) and crystallization temperature T_(c) weremeasured on approx. 5 mg samples with a Mettler-Toledo 822e differentialscanning calorimeter (DSC), according to ISO11357-3 in a heat/cool/heatcycle with a scan rate of 10° C./min in the temperature range of +23 to+225° C. under a nitrogen flow rate of 50 ml min⁻¹. Melting andcrystallization temperatures were taken as the endotherm and exothermpeaks, respectively in the second heating and in the cooling step.Calibration of the instrument was performed with H₂O, Lead, Tin, Indium,according to ISO 11357-1.

Melt Flow Rate

The melt flow rate (MFR) is determined according to ISO 1133 and isindicated in g/10 min. The MFR is an indication of the flowability, andhence the processability, of the molten polymer. The higher the meltflow rate, the lower the viscosity of the polymer. The MFR is determinedat 230° C. and may be determined at different loadings such as 2.16 kg(MFR₂) or 21.6 kg (MFR₂₁).

GPC: Molecular weight averages, molecular weight distribution, andpolydispersity index (M_(e), M_(w), M_(w)/M_(n))

Molecular weight averages (Mw, Mn), Molecular weight distribution (MWD)and its broadness, described by polydispersity index, PDI=Mw/Mn (whereinMn is the number average molecular weight and Mw is the weight averagemolecular weight) were determined by Gel Permeation Chromatography (GPC)according to ISO 16014-4:2003 and ASTM D 6474-99. A Waters GPCV2000instrument, equipped with differential refractive index detector andonline viscosimeter was used with 2×GMHXL-HT and 1× G7000HXL-HT TSK-gelcolumns from Tosoh Bioscience and 1,2,4-trichlorobenzene (TCB,stabilized with 250 mg/L 2,6-Di tert butyl-4-methyl-phenol) as solventat 140° C. and at a constant flow rate of 1 mL/min. 209.5 μL of samplesolution were injected per analysis. The column set was calibrated usinguniversal calibration (according to ISO 16014-2:2003) with at least 15narrow MWD polystyrene (PS) standards in the range of 1 kg/mol to 12 000kg/mol. Mark Houwink constants for PS, PE and PP used are as per ASTM D6474-99. All samples were prepared by dissolving 0.5-4.0 mg of polymerin 4 mL (at 140° C.) of stabilized TCB (same as mobile phase) andkeeping for max. 3 hours at max. 160° C. with continuous gentle shakingprior sampling into the GPC instrument.

Quantification of Polypropylene Homopolymer Microstructure by NMRSpectroscopy

Quantitative nuclear-magnetic resonance (NMR) spectroscopy was used toquantify the isotacticity and content of regio-defects of thepolypropylene homopolymers. Quantitative ¹³C{¹H} NMR spectra recorded inthe solution-state using a Bruker Advance III 400 NMR spectrometeroperating at 400.15 and 100.62 MHz for ¹H and ¹³C respectively. Allspectra were recorded using a ¹³C optimised 10 mm selective excitationprobehead at 125° C. using nitrogen gas for all pneumatics.Approximately 200 mg of material was dissolved in1,2-tetrachloroethane-d₂ (TCE-d₂). This setup was chosen primarily forthe high resolution needed for tacticity distribution quantification(Busico, V., Cipullo, R., Prog. Polym. Sci. 26 (2001) 443; Busico, V.;Cipullo, R., Monaco, G., Vacatello, M., Segre, A. L., Macromolecules 30(1997) 6251). Standard single-pulse excitation was employed utilisingthe NOE and bi-level WALTZ16 decoupling scheme (Zhou, Z., Kuemmerle, R.,Qiu, X., Redwine, D., Cong, R., Taha, A., Baugh, D. Winniford, B., J.Mag. Reson. 187 (2007) 225; Busico, V., Carbonniere, P., Cipullo, R.,Pellecchia, R., Severn, J., Talarico, G., Macromol. Rapid Commun 2007,28, 11289). A total of 8192 (8 k) transients were acquired per spectra.Quantitative ¹³C{¹H} NMR spectra were processed, integrated and relevantquantitative properties determined from the integrals using proprietarycomputer programs. All chemical shifts are internally referenced to themethyl signal of the isotactic pentad mmmm at 21.85 ppm.

The tacticity distribution was quantified through integration of themethyl region between 23.6 and 19.7 ppm correcting for any sites notrelated to the stereo sequences of interest (Busico, V., Cipullo, R.,Prog. Polym. Sci. 26 (2001) 443; Busico, V., Cipullo, R., Monaco, G.,Vacatello, M., Segre, A. L., Macromolecules 30 (1997) 6251). The pentadisotacticity was determined through direct integration of the methylregion and reported as either the mole fraction or percentage ofisotactic pentad mmmm with respect to all steric pentads i.e.[mmmm]=mmmm/sum of all steric pentads. When appropriate integrals werecorrected for the presence of sites not directly associated with stericpentads.

Characteristic signals corresponding to regio irregular propeneinsertion were observed (Resconi, L., Cavallo, L., Fait, A., Piemontesi,F., Chem. Rev. 2000, 100, 1253). The presence of secondary insertedpropene in the form of 2,1 erythro regio defects was indicated by thepresence of the two methyl signals at 17.7 and 17.2 ppm and confirmed bythe presence of other characteristic signals. The amount of 2,1 erythroregio defects was quantified using the average integral (e) of the e6and e8 sites observed at 17.7 and 17.2 ppm respectively, i.e.e=0.5*(e6+e8). Characteristic signals corresponding to other types ofregio irregularity were not observed (Resconi, L., Cavallo, L., Fait,A., Piemontesi, F., Chem. Rev. 2000, 100, 1253). The amount of primaryinserted propene (p) was quantified based on the integral of all signalsin the methyl region (CH3) from 23.6 to 19.7 ppm paying attention tocorrect for other species included in the integral not related toprimary insertion and for primary insertion signals excluded from thisregion such that p=CH3+2*e. The relative content of a specific type ofregio defect was reported as the mole fraction or percentage of saidregio defect with respect all observed forms of propene insertion i.e.sum of all primary (1,2), secondary (2,1) and tertiary (3,1) insertedpropene units, e.g. [21e]=e/(p+e+t+i). The total amount of secondaryinserted propene in the form of 2,1-erythro or 2,1-threo regio defectswas quantified as sum of all said regio irregular units, i.e.[21]=[21e]+[21t].

Catalyst Activity

The catalyst activity (A Cat) was calculated on the basis of followingformula:

$ {{Catalyst}\mspace{14mu} {Activity}\mspace{14mu} ({kg})\text{/}( {{g({cat})}*h} )} ) = \frac{{amount}\mspace{14mu} {of}\mspace{14mu} {polymer}\mspace{14mu} {produced}\mspace{14mu} ({kg})}{{catalyst}\mspace{14mu} {loading}\mspace{14mu} (g) \times {polymerisation}\mspace{14mu} {time}\mspace{14mu} (h)}$

Catalyst Metal Activity (A Mt) was calculated on the basis of followingformula:

${{Catalyst}\mspace{14mu} {Metal}\mspace{14mu} {Activity}\mspace{14mu} ( {{kg}\text{/}( {{g({cat})}*h} )} )} = \frac{{amount}\mspace{14mu} {of}\mspace{14mu} {polymer}\mspace{14mu} {produced}\mspace{14mu} ({kg})}{{catalyst}\mspace{14mu} {metal}\mspace{14mu} {loading}\mspace{14mu} (g) \times {polymerisation}\mspace{14mu} {time}\mspace{14mu} (h)}$

EXAMPLES Chemicals

All the chemicals and chemical reactions were handled under an inert gasatmosphere using Schlenk and glovebox techniques, with oven-driedglassware, syringes, needles or cannulas.

MAO was purchased from Albermarle and used as a 30 wt-% solution intoluene.

The mixture of perfluoroalkylethyl acrylate esters (CAS 65605-70-1) usedas the surfactant was purchased from the Cytonix corporation, dried overactivated molecular sieves (2 times) and degassed by argon bubblingprior to use.

Perfluoro-1,3-dimethylcyclohexane (PFC, CAS 335-27-3) was dried overactivated molecular sieves (2 times) and degassed by argon bubblingprior to use.

Triethylaluminum was purchased from Crompton and used in pure form.Hydrogen is provided by AGA and purified before use.

Propylene is provided by Borealis and adequately purified before use. 2M HCl, 12 M HCl (Reachim, Russia), silica gel 60 (40-63 um, Merck),K₂CO₃ (Merck), ZrCl₄(THF)₂ magnesium turnings (Acros), TsOH (Aldrich),nBuLi (Chemetall), n-hexane (Merck), were used as received. Toluene(Merck), THF (Merck), dichloromethane (Merck), were kept and distilledover Na/K alloy. Dichlorodimethylsilane (Merck) was distilled beforeuse. CDCl₃, DMSO-d₆ and CD₂Cl₂ (Deutero GmbH) for NMR experiments weredried and kept over CaH₂. methyl iodide (Acros)1-bromo-3,5-di-tert-butylbenzene (Aldrich) has been used as received.Bis(2,6-diisopropylphenyl)imidazolium chloride, i.e. IPr(HCl), and(IPr)NiCl₂(PPh₃) were synthesized as described in [Hintermann, L.Beilstein J. Org. Chem. 2007, 3, 1.] and [Matsubara, K.; Ueno, K.;Shibata, Y. Organometallics 2006, 25, 3422.], respectively.4-Bromo-1-methoxy-2-methylindane was obtained as described in [Izmer, V.V.; Lebedev, A. Y.; Nikulin, M. V.; Ryabov, A. N.; Asachenko, A. F.;Lygin, A. V.; Sorokin, D. A.; Voskoboynikov, A. Z. Organometallics 2006,25, 1217.].

-   -   rac-dimethylsilanediylbis(2-methyl-4-phenylindenyl) zirconium        dichloride, is described e.g. in EP-A-0576970, has CAS no        153882-67-8 and provided by Norquaytech.

rac-dimethylsilanediylbis(2-methyl-4-(3,5-di-tert-butylphenyl)-7-methoxyindenyl)zirconium dichloride, has been synthesized as described by Schöbel,Rieger et al. in Chemistry-A European Journal, vol. 18, pages 4174-4178(2012).

Catalyst Preparation 1 Catalyst complex synthesis ofrac-Me₂Si[2-Me-4-(3,5-^(t)Bu₂Ph)Ind]₂ZrCl₂—MC17-(3,5-di-tert-butylphenyl)-2-methyl-1H-indene

To a solution of 3,5-di-tert-butylphenylmagnesium bromide obtained from29.6 g (0.110 mol) of 1-bromo-3,5-di-tert-butylbenzene and 3.80 g (0.156mol) of magnesium turnings in 200 ml of THF, 0.40 g (0.512 mmol, 0.5mol.%) of NiCl₂(PPh₃)(IPr) and 24.1 g (0.10 mol) of4-bromo-1-methoxy-2-methylindane were added. A vigorous reflux occurredapproximately after 30 sec which ceased after the following 30 sec. Thismixture was stirred at room temperature for 30 min. Finally, 1000 ml ofwater and then 50 ml of 12 M HCl were added. The product was extractedwith 500 ml of dichloromethane, organic layer was separated, the aqueouslayer was additionally extracted with 2×150 ml of dichloromethane. Thecombined organic extract was dried over K₂CO₃ and evaporated to dryness.To the residue dissolved in 300 ml of toluene 0.4 g of TsOH was added.The resulting solution was refluxed using Dean-Stark head for 15 min,then another 0.5 g of TsOH was added, and the obtained mixture wasrefluxed for 0.5 h. The reaction mixture was cooled to room temperatureand then washed by 200 ml of 10% aqueous K₂CO₃.

The organic layer was separated, the aqueous layer was additionallyextracted with 2×100 ml of dichloromethane. The combined organic extractwas evaporated to dryness. The product was isolated by flashchromatography on silica gel 60 (40-63 μm; eluent: hexane, thenhexane/dichloromethane=10:1, vol.). This procedure gave 31.9 g (99%) of7-(3,5-di-tert-butylphenyl)-2-methyl-1H-indene as a white crystallinepowder. The latter was recrystallized from n-hexane with almost no lossin mass.

Anal. calc. for C₂₄H₃₀: C, 90.51; H, 9.49. Found: C, 90.48; H, 9.44.

¹H NMR (CDCl₃): δ 7.41 (t, J=1.8 Hz, 1H, 4-H in 3,5-tBu₂C₆H₃), 7.37 (d,J=1.8 Hz,

2H, 2,6-H in 3,5-tBu₂C₆H₃), 7.31 (t, J=7.5 Hz, 1H, 5-H in indene), 7.24(dd, J=7.5 Hz, J=1.0

Hz, 1H, 6-H in indene), 7.15 (dd, J=7.5 Hz, J=1.1 Hz, 1H, 4-H inindene), 6.54 (m, 1H, 3-H in

indene), 3.38 (m, 2H, 1,1′-H in indene), 2.14 (m, 3H, 2-Me in indene),1.38 (s, 18H, tBu).

Bis[4-(3,5-di-tert-butylphenyl)-2-methyl-1H-inden-1-yl]dimethylsilane

15.0 ml (37.5 mmol) of 2.5 M nBuLi in hexanes was added in one portionat room temperature to a solution of 11.9 g (37.5 mmol) of7-(3,5-di-tert-butylphenyl)-2-methyl-1H-indene in 200 ml of toluene.This mixture was stirred overnight at room temperature, then 10 ml ofTHF was added, and the resulting mixture was refluxed for 2 h. Theresulting mixture was cooled to room temperature, and 2.42 g (18.8 mmol)of dichlorodimethylsilane was added in one portion. Further on, thismixture was refluxed for 1 h, then 0.5 ml of water was added, and theformed solution was filtered through a pad of silica gel 60 (40-63 μm)which was additionally washed by dichloromethane. The combined organicelute was evaporated to dryness and dried in vacuum. This procedure gave13.0 g (100% of ca. 90% purity) ofbis[4-(3,5-di-tert-butylphenyl)-2-methyl-1H-inden-1-yl]dimethylsilane asa yellowish glass. This product was further used without an additionalpurification.

Anal. calc. for C₅₀H₆₄Si: C, 86.64; H, 9.31. Found: C, 87.05; H, 9.55.

¹H NMR (CDCl3): δ 7.21-7.57 (m), 6.89 (m), 6.88 (m), 3.91 (s), 3.87 (s),2.31 (s), 2.29

(s), 1.45 (s), 1.44 (s), −0.13 (s), −0.15 (s), −0.19 (s).

Rac-dimethylsilanediylbis[4-(3,5-di-tert-butylphenyl)-2-methyl-1H-inden-1-yl]zirconiumdichloride (Complex MC1)

To a solution of 10.7 g (15.4 mmol) ofbis[4-(3,5-di-tert-butylphenyl)-2-methyl-1H-inden-1-yl]dimethylsilane in150 ml of toluene, 12.3 ml (30.8 mmol) of 2.5 M nBuLi in hexanes wasadded in one portion at room temperature. This mixture was stirredovernight at room temperature, the resulting light orange solution wasthen cooled to −25° C., and 5.81 g (15.4 mmol) of ZrCl₄(THF)₂ was added.The resulting dark red mixture was stirred for 24 h, then 10 ml of THFwas added. The obtained mixture was stirred for 2 h at 60° C. Afterevaporation of ca. 50 ml of the solvents, the resulting solution warmedto 80° C. was filtered through glass frit (G4). The filtrate wasevaporated to dryness, and then 250 ml of n-hexane was added to theresidue. The obtained suspension was stirred overnight at roomtemperature and then filtered through a glass frit (G3). The filtratewas evaporated to dryness, and 25 ml of n-hexane was added to theresidue. The formed yellow precipitate was filtered off, washed with5×15 ml of n-hexane, and dried in vacuum. This procedure gaverac-zirconocene contaminated with ca. 4% of meso-form. To purify it,this product was dissolved in 20 ml of hot toluene, and to the obtainedsolution 100 ml of n-hexane was added. The formed precipitate wasfiltered off and then dried in vacuum. This procedure gave 2.29 g (17%)of pure rac-complex.

Anal. calc. for C₅₀H₆₂Cl₂SiZr: C, 70.38; H, 7.32. Found: C, 70.29; H,7.38.

¹H NMR (CDCl₃): δ 7.66 (d, J=8.4 Hz, 2H, 5-H in indenyl), 7.54 (m, 4H,2,6-H in 3,5-tBu₂C₆H₃), 7.40-7.43 (m, 4H, 7-H in indenyl and 4-H in3,5-tBu₂C₆H₃), 7.12 (dd, J=8.4 Hz, J=6.9 Hz, 2H, 6-H in indenyl), 6.97(s, 2H, 3-H in indenyl), 2.26 (s, 6H, 2-Me in indenyl), 1.34 (s, 6H,SiMe₂), 1.32 (s, 36H, tBu).

Catalyst Example E1 rac-Me₂Si[2-Me-4-(3,5-^(t)Bu₂Ph)Ind]₂ZrCl₂ (MC1)

Inside the glovebox, 80 μL, of dry and degassed surfactant solution weremixed with 2 mL of MAO in a septum bottle and left to react overnight.The following day, 64.9 mg of the metallocenerac-Me₂Si[2-Me-4-(3,5-^(t)Bu₂Ph)Ind]₂ZrCl₂/MAO (0.076 mmol, 1equivalent) were dissolved with 4 mL of the MAO solution in anotherseptum bottle and left to stir inside the glovebox.

After 60 minutes, 1 mL of the surfactant solution and the 4 mL of theMAO-metallocene solution were successively added into a 50 mLemulsification glass reactor containing 40 mL of PFC at −10° C. andequipped with an overhead stirrer (stirring speed=600 rpm). Total amountof MAO is 5 mL (300 equivalents). A red-orange emulsion formedimmediately (measured emulsion stability=17 seconds) and stirred during15 minutes at 0° C./600 rpm. Then the emulsion was transferred via a 2/4teflon tube to 100 mL of hot PFC at 90° C., and stirred at 600 rpm untilthe transfer is completed, then the speed was reduced to 300 rpm. After15 minutes stirring, the oil bath was removed and the stirrer turnedoff. The catalyst was left to settle up on top of the PFC and after 45minutes the solvent was siphoned off. The remaining red catalyst wasdried during 2 hours at 50° C. over an argon flow. 0.45 g of a red freeflowing powder was obtained.

Comparative Example CE1

as metallocene is usedrac-dimethylsilanediylbis(2-methyl-4-phenylindenyl) zirconium dichloride

Inside the glovebox, 80 μL, of dry and degassed surfactant solution weremixed with 2 mL of MAO in a septum bottle and left to react overnight.The following day, 47.8 mg of the metallocene.rac-dimethylsilanediylbis(2-methyl-4-phenylindenyl) zirconiumdichloride, (0.076 mmol, 1 equivalent) were dissolved with 4 mL of theMAO solution in another septum bottle and left to stir inside theglovebox.

After 60 minutes, 1 mL of the surfactant solution and the 4 mL of theMAO-metallocene solution were successively added into a 50 mLemulsification glass reactor containing 40 mL of PFC at −10° C. andequipped with an overhead stirrer (stirring speed=600 rpm). Total amountof MAO is 5 mL (300 equivalents). A red-orange emulsion formedimmediately (measured emulsion stability=20 seconds) and stirred during15 minutes at 0° C./600 rpm.

Then the emulsion was transferred via a 2/4 teflon tube to 100 mL of hotPFC at 90° C., and stirred at 600 rpm until the transfer is completed,then the speed was reduced to 300 rpm. After 15 minutes stirring, theoil bath was removed and the stirrer turned off. The catalyst was leftto settle up on top of the PFC and after 45 minutes the solvent wassiphoned off. The remaining red catalyst was dried during 2 hours at 50°C. over an argon flow. 0.51 g of a red free flowing powder was obtained.

Comparative Example CE2

as metallocene is used rac-Me₂Si[2-Me-4-(3,5-^(t)Bu₂Ph)-7-OMe-Ind]₂ZrCl₂

Inside the glovebox, 80 μL of dry and degassed surfactant solution weremixed with 2 mL of MAO in a septum bottle and left to react overnight.The following day, 69.4 mg of the metallocene,rac-Me₂Si[2-Me-4-(3,5-^(t)Bu₂Ph)-7-OMe-Ind]₂ZrCl₂/MAO, (0,076 mmol, 1equivalent) were dissolved with 4 mL of the MAO solution in anotherseptum bottle and left to stir inside the glovebox.

After 60 minutes, 1 mL of the surfactant solution and the 4 mL of theMAO-metallocene solution were successively added into a 50 mLemulsification glass reactor containing 40 mL of PFC at −10° C. andequipped with an overhead stirrer (stirring speed=600 rpm). Total amountof MAO is 5 mL (300 equivalents). A red-orange emulsion formedimmediately (measured emulsion stability=16 seconds) and stirred during15 minutes at 0° C./600 rpm. Then the emulsion was transferred via a 2/4teflon tube to 100 mL of hot PFC at 90° C., and stirred at 600 rpm untilthe transfer is completed, then the speed was reduced to 300 rpm. After15 minutes stirring, the oil bath was removed and the stirrer turnedoff. The catalyst was left to settle up on top of the PFC and after 45minutes the solvent was siphoned off. The remaining red catalyst wasdried during 2 hours at 50° C. over an argon flow. 0.74 g of a red freeflowing powder was obtained.

Catalyst properties are described in Table 1

TABLE 1 Catalyst name Zr (%) Al (%) Al/Zr (molar) E1 0.29 24.0 280 CE10.25 18.6 251 CE2 0.29 23.70 276

Polymerisations

The polymerisations were performed in a 5 L reactor. 200 μl oftriethylaluminum was fed as a scavenger in 5 mL of dry and degassedpentane. The desired amount of hydrogen was then loaded (measured inmmol) and 1100 g of liquid propylene was fed into the reactor.

Procedure A: The temperature was set to 30° C. The desired amount ofcatalyst (3 to 30 mg) in 5 mL of PFC is flushed into the reactor with anitrogen overpressure. The temperature is then raised to 70° C. over aperiod of 15 minutes. The polymerisation is stopped after 30 minutes byventing the reactor and flushing with nitrogen before the polymer iscollected.

Procedure B: The temperature was set to 20° C. The desired amount ofcatalyst (3 to 30 mg) in 5 mL of PFC is flushed into the reactor with anitrogen overpressure. After 5 minutes of the temperature is raised to70° C. over a period of 15 minutes. The polymerisation is stopped after60 minutes by venting the reactor and flushing with nitrogen before thepolymer is collected.

The catalyst activity (A Cat) was calculated on the basis of the 30 (or60) minutes period according to the following formula:

${{Catalyst}\mspace{14mu} {Activity}\mspace{14mu} ( {{kg}\text{/}( {{g({cat})}*h} )} )} = \frac{{amount}\mspace{14mu} {of}\mspace{14mu} {polymer}\mspace{14mu} {produced}\mspace{14mu} ({kg})}{{catalyst}\mspace{14mu} {loading}\mspace{14mu} (g) \times {polymerisation}\mspace{14mu} {time}\mspace{14mu} (h)}$

Catalyst Metal Activity (A Mt) was calculated on the basis of followingformula:

${{Catalyst}\mspace{14mu} {Metal}\mspace{14mu} {{Activity}{\; \mspace{11mu}}( {{kg}\text{/}( {{g({cat})}*h} )} )}} = \frac{{amount}\mspace{14mu} {of}\mspace{14mu} {polymer}\mspace{14mu} {{produced}{\; \mspace{11mu}}({kg})}}{{catalyst}\mspace{14mu} {metal}\mspace{14mu} {loading}\mspace{14mu} (g) \times {polymerisation}\mspace{14mu} {time}\mspace{14mu} (h)}$

Polymerisation results are disclosed in table 2

TABLE 2 polymerization results with catalyst CE1, CE2 and E1 CatalystCat. Time H₂ Pol. A cat A Mt MFR₂ M_(w) M_(w)/ T_(m) T_(c) Type (mg) minmmol Yield, g kg/g/h kg/gMt/h g/10⁶ kg/mol M_(n) (° C.) (° C.) CE1 13.530 1 61 9.1 3639 3.6** 676 2.4 149.3 110.5 12.3 30 6 80 13.1 5229 53.0**392 2.3 151.3 109.3 32.4 30 15 329 20.3 8116 4.5 240 2.4 150.0 109.7 CE218.3 30 1 50 5.5 1888 1.9 347 2.0 159.4 113.5 16.1 30 6 120 15.0 515719.0 190 2.1 156.2 113.8 13.6 30 15 114 16.8 5781 120 106 2.2 156.6116.5 E1 11.1 60* 1 99 9.0 3088 9.4** 574 2.5 156.5 111.9 5.5 60* 6 10018.2 6270 1.9 302 2.4 158.9 112.2 10.7 60* 15 218 20.4 7025 21.0 179 2.4156.6 112.7 *procedure B, **MFR₂₁ (g/10 min)

As can be seen higher Tm and at the same time higher activity areobtained by the catalyst of the invention.

NMR results are disclosed in Table 3

Catalyst mmmm % 2,1e % E1 99.35 0.41 CE1 99.14 0.98 CE2 99.06 0.45

Comparative Example CE3 and CE4 Conventionally silica supportedrac-Me₂Si[2-Me-4-(3,5-^(t)Bu₂Ph)Ind]₂ZrCl₂

Melting temperature and activity of the catalyst of the invention can befurther compared to the catalyst of the same metallocene complex (MC-1),but supported on silica support. This supported catalyst has beendisclosed in WO02/02576. Results are disclosed in Tables 6 and 8 ofWO02/02576, and for comparison are used results of examples 32 and 42 ofWO02/02576.

Catalyst Performance

As shown in Table 4 below, the catalyst of the invention showssignificantly higher activity, at comparable MFR, than the comparisoncatalysts CE3, CE4 and CE2, while maintaining the high melting point.

TABLE 4

Ligand CE3 CE4 CE2 E1-invention cocatalyst MAO Borate MAO MAO carrierSiO₂ SiO₂ Solid no carrier Solid no carrier T_(p)* 70 70 70 70 MFR 6.914.7 19 21 T_(m) 157.4 159.1 156.2 156.6 kg/g(cat)/h 6.0 4.9 15.0 20.4kg/g(Zr)/h 3300 5160 7025 source WO0202576 WO0202576 CE2 This inventionTab 6, Ex 32 Tab 8, ex 42 T_(p)* = polymerisation temperature

1. A catalyst in solid particulate form free from an external carriermaterial comprising (i) a complex of formula (I)

wherein M is zirconium or hafnium; each X is a sigma ligand; L is adivalent bridge selected from the group consisting of —R′₂C—,—R′₂C—CR′₂—, —R′₂Si—, —R′₂Si—SiR′₂—, —R′₂Ge—, wherein each R′ isindependently a hydrogen atom, C1-C20-alkyl, tri(C1-C20-alkyl)silyl,C6-C20-aryl, C7-C20-arylalkyl and C7-C20-alkylaryl; each R₂ isindependently hydrogen or a C1-C20 hydrocarbyl radical provided that atleast one R₂ is not hydrogen; each R₅ is independently hydrogen or aC1-20 hydrocarbyl group optionally containing one or more heteroatomsfrom groups 14-16; each R₆ is independently hydrogen or a C1-20hydrocarbyl group optionally containing one or more heteroatoms fromgroups 14-16; each n is independently 1, 2 or 3; and each R₈ is a C1-20hydrocarbyl group; and (ii) a cocatalyst comprising a compound of agroup 13 metal.
 2. The catalyst of claim 1 which is obtainable by aprocess in which (a) a liquid/liquid emulsion system is formed, saidliquid/liquid emulsion system comprising a solution of the catalystcomponents (i) and (ii) dispersed in a solvent so as to form disperseddroplets; and (b) solid particles are formed by solidifying saiddispersed droplets.
 3. A catalyst as claimed in claim 1 comprising acomplex of formula

wherein M is zirconium or hafnium; each X is a sigma ligand; L is adivalent bridge selected from the group consisting of —R′₂C—,—R′₂C—CR′₂—, —R′₂Si—, —R′₂Si—SiR′₂—, —R′₂Ge—, wherein each R′ isindependently a hydrogen atom, C1-C20-alkyl, tri(C1-C20-alkyl)silyl,C6-C20-aryl, C7-C20-arylalkyl and C7-C20-alkylaryl; each R₂ isindependently hydrogen or a C1-C20 hydrocarbyl radical provided that atleast one R₂ is not hydrogen; each R₅ is independently hydrogen or analiphatic C1-20 hydrocarbyl group; each R₆ is independently hydrogen oran aliphatic C1-20 hydrocarbyl group; n is 1, 2 or 3; and each R₈ is analiphatic C1-20 hydrocarbyl group.
 4. A catalyst as claimed in claim 1comprising a complex of formula (II)

wherein M is zirconium or hafnium; each X is independently a hydrogenatom, a halogen atom, C₁₋₆-alkoxy group, C₁₋₆-alkyl, phenyl or benzylgroup; L is a divalent bridge selected from the group consisting of—R′₂C—, —R′₂C—CR′₂—, —R′₂Si—, —R′₂Si—SiR′₂—, —R′₂Ge—, wherein each R′ isindependently a hydrogen atom, C1-C20-alkyl, tri(C1-C20-alkyl)silyl,C6-C20-aryl, C7-C20-arylalkyl and C7-C20-alkylaryl; each R₂ is a C1-10alkyl group; each R₅ is hydrogen or a C1-10 alkyl group; each R₆ ishydrogen or a C1-10 alkyl group; n is 1 to 3; and each R⁸ is a C1-20hydrocarbyl group.
 5. A catalyst as claimed in claim 1 comprising acomplex of formula (III):

wherein M is zirconium or hafnium; each X is independently a hydrogenatom, a halogen atom, C₁₋₆-alkoxy group, C₁₋₆-alkyl, phenyl or benzylgroup; L is a divalent bridge selected from the group consisting of—R′₂C—, —R′₂C—CR′₂—, —R′₂Si—, —R′₂Si—SiR′₂—, —R′₂Ge—, wherein each R′ isindependently a hydrogen atom, C1-C20-hydrocarbyl,tri(C1-C20-alkyl)silyl, C6-C20-aryl, C7-C20-arylalkyl andC7-C20-alkylaryl; R₂ is preferably a C1-10 alkyl group; n is 1 to 3; andeach R⁸ is a C1-10 alkyl group or C6-10 aryl group.
 6. A catalyst asclaimed in claim 1 comprising a complex of formula (IV)

wherein L, M and X are as hereinbefore defined; R₂ is methyl; and R₈ isC3-8 alkyl.
 7. A catalyst as claimed in claim 1 wherein L isdimethylsilyl, ethylene or methylene.
 8. A catalyst as claimed in claim1 comprising the complex rac-Me₂Si[2-Me-4(3,5-^(t)Bu₂Ph)-Ind]₂ZrCl₂ orrac-Me₂Si[2-Me-4(3,5-^(t)Bu₂Ph)-Ind]₂HfCl₂.
 9. A catalyst as claimed inclaim 1 wherein said cocatalyst is aluminoxane, preferably MAO.
 10. Acatalyst as claimed in claim 1 wherein the two ligands forming thecomplex are identical.
 11. A process for the preparation of a compoundof formula (V):

comprising at least the step of reacting a compound of formula (VI)

with a compound (VII)

wherein R₂, R₅, R₆, R₈ and n are as herein before defined in claim 1;and Hal is a halide; in the presence of PPh₃IPrNiCl₂.
 12. A process asclaimed in claim 11 wherein said compound of formula (V) is


13. A process for the manufacture of a catalyst as claimed in claim 1comprising obtaining a (i) complex of formula (I) and (ii) a cocatalystcomprising a compound of a group 13 metal; forming a liquid/liquidemulsion system, which comprises a solution of catalyst components (i)and (ii) dispersed in a solvent, and solidifying said dispersed dropletsto form solid particles.
 14. A process for the polymerisation of atleast one olefin comprising polymerising said at least one olefin withthe catalyst as claimed in claim
 1. 15. A process as claimed in claim 14wherein the process forms an isotactic polypropylene.
 16. A process asclaimed in claim 15 wherein the catalyst activity in said process is atleast 10.0 kg/g(cat)/h.